EP0802965A1 - Detergent seche par pulverisation ou constituant pour celui-ci - Google Patents

Detergent seche par pulverisation ou constituant pour celui-ci

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Publication number
EP0802965A1
EP0802965A1 EP95942725A EP95942725A EP0802965A1 EP 0802965 A1 EP0802965 A1 EP 0802965A1 EP 95942725 A EP95942725 A EP 95942725A EP 95942725 A EP95942725 A EP 95942725A EP 0802965 A1 EP0802965 A1 EP 0802965A1
Authority
EP
European Patent Office
Prior art keywords
weight
spray
dried
detergent
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95942725A
Other languages
German (de)
English (en)
Other versions
EP0802965B1 (fr
Inventor
Fred Schambil
Wolfram Linke
Hubert Freese
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the invention relates to a spray-dried detergent or a component therefor, the spray-dried detergent or the component therefor having both good washing-in behavior and good dissolving behavior.
  • the invention also relates to a washing method, in which the spray-dried detergent is washed into a commercially available washing machine via a washing-in chamber.
  • nonionic surfactants have a very high cleaning power, which makes them particularly suitable for use at washing temperatures of 60 ° C. and below.
  • nonionic surfactants can only be processed by spray drying in certain quantities, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and poor sprayability of the spray powder.
  • anionic surfactants when incorporated into the slurry in the presence of anionic surfactants, they undesirably increase its viscosity. Processes have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried grain or sprayed onto a carrier substance.
  • EP-A-0 360 330 it is known from European patent application EP-A-0 360 330 to spray mixtures of nonionic surfactants and fatty acids onto a spray-dried base powder, the spray-dried base powder containing phosphates, and to treat the treated spray-dried grain with substances such as carbonate.
  • Spray-dried carrier grains which have been after-treated with nonionic surfactants are known, for example, from European patent application EP-A-0 149264 and German patent applications DE-A-3444960, DE-A-3545947 and DE-A-3936405.
  • the object of the invention was therefore to provide a spray-dried detergent which has both good wash-in behavior and good dissolving behavior.
  • the invention relates in a first embodiment to a spray-dried detergent or a component therefor, comprising anionic surfactants, inorganic fluoride substances and other constituents of detergents, the agent in the spray-dried particle a) 3 to 20% by weight Anionic surfactants, b) 0 to 2% by weight of nonionic surfactants, c) 20 to 65% by weight of inorganic builder substances (based on anhydrous active substance) from the group of carbonates, bicarbonates and silicate builder substances, d) 0 to 25% by weight .-% neutral salts, e) contains other conventional ingredients with the proviso that the spray-dried grain is aftertreated with nonionic surfactants.
  • the quantities a) to e) relate to the spray-dried grain which has not been treated, unless otherwise stated in the text.
  • spray-dried detergents or components therefor are claimed in which the weight ratio of the spray-dried grain to the nonionic surfactant is 10: 1 to 25: 1 and in particular 12: 1 to 20: 1.
  • the agents contain, as inorganic builder substances c), at least one silicate builder, in particular aluminosilicates and / or amorphous sodium and / or potassium silicates.
  • the agents advantageously contain at least one silicate builder in combination with sodium and / or potassium carbonate.
  • aluminosilicates are fine-crystalline, synthetic and bound water-containing zeolites, such as zeolite A in detergent quality.
  • zeolite X and zeolite P and mixtures of zeolite A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on the zeolite, of ethoxylated Ci2-Ci8-fatty alcohols with 2 to 5 ethylene oxide.
  • Suitable powdered zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • sodium silicates with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are particularly suitable.
  • the content of the spray-dried grain of alkali carbonates and / or hydrogen carbonates, in particular sodium carbonates and / or sodium hydrogen carbonates, is preferably 3 to 25% by weight and in particular 10 to 25% by weight, while amorphous silicates, in particular sodium silicates, contain one Na2 ⁇ : Si ⁇ 2 ratio of 1: 2 to 1: 3.5 is advantageously contained in amounts of 0.5 to 7.5% by weight, based on the spray-dried grain.
  • zeolite can vary widely in the spray-dried grain. Embodiments which contain more than 30% by weight and in particular at least 35% by weight of zeolite (based on anhydrous active substance) are preferred, as are embodiments which contain a maximum of 30% by weight zeolite (based on anhydrous active substance) exhibit. In the latter cases, it is preferred that additional builders are added to the spray-dried grain aftertreated with nonionic surfactants.
  • the spray-dried grain is post-treated with nonionic surfactants, this post-treatment being carried out by spraying the nonionic surfactants or an aqueous solution or dispersion of nonionic surfactants onto the spray-dried grain.
  • Spraying can be carried out once, several times or continuously, for example on conveyor belts.
  • preference is given to a procedure in which nonionic surfactants are mixed with the spray-dried grain in a mixer or the nonionic surfactants in a mixer onto the spray-dried grain be sprayed on.
  • the grain can be compacted in this mixer, which causes an increase in the bulk density.
  • the non-ionic surfactants used in the aftertreatment are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in the 2-position May be methyl-branched or line-are and may contain methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohols with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to, methyl-branched radicals 18 carbon atoms means and G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10 and is preferably 1.1 to 1.4.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated alcohols, in particular not more than half of them.
  • polyhydroxy fatty acid amides which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanol and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the spray-dried grain itself should not contain more than 2% by weight of nonionic surfactants.
  • the spray-dried grain preferably contains only a maximum of 1% by weight of nonionic surfactants before its aftertreatment. It is even preferred that these nonionic surfactants are not added to the slurry, but only via raw materials used, in which they contain e.g. B. are used as stabilizers, are introduced into the spray-dried slurry.
  • the non-ionic surfactants here in turn are primarily the alkoxylated, preferably ethoxylated alcohols and fatty alcohols, and also alkyl glycosides and polyhydroxy fatty acid amides.
  • the grain to be spray-dried contains anionic surfactants in amounts of 3 to 20% by weight, with amounts of 5 to 15% by weight being preferred.
  • the anionic surfactants used are, in particular, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are Cg-C ⁇ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 -C 8 -monoolefins with a terminal or internal double bond by sulfo- kidneys with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or
  • esters of ⁇ -sulfofatty acids for example oc-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and the ⁇ -sulfofatty acids or their di-salts obtainable from these by ester cleavage.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • sulfonation products are a complex mixture that contains mono-, di- and triglyceride sulfonates with an ⁇ -and / or internal-sulfonic acid grouping.
  • sulfonated fatty acid salts As by-products, sulfonated fatty acid salts, glyceride sulfates, Glycerin sulfates, glycerin and soaps. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the alkali and especially the sodium salts of the sulfuric acid half esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ⁇ o-C2 ⁇ _ 0xoalcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ciss-CJ ⁇ -alk (en) yl sulfates are particularly preferred from the point of view of washing technology.
  • Ci6-Ci8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower point of action and at relatively low washing temperatures of for example, room temperature to 40 ° C show a lower tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2-Ci4-fatty alkyl sulfates or C ⁇ 2-Ci8-fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ci ⁇ -Ci ⁇ -Fatty alkyl sulfates.
  • not only saturated alkyl sulfates, but also unsaturated alkyl sulfates with an alkenyl chain length of preferably Ciö to C22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of EO or Ci2-Ci8 fat alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain CQ to Ci8 ⁇ fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from fatty alcohols which, viewed in isolation, are nonionic surfactants.
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred anionic surfactant mixtures contain combinations with alk (en) yl sulfates, in particular combinations of alk (en) yl sulfates and alkylbenzenesulfonates.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the agents can also contain soaps, preferably in amounts of at most 5% by weight, in particular in amounts of Contain 0.5 to 3 wt .-%.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the soaps are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the preferred neutral salts include sodium sulfates and / or potassium sulfates, which are known to be advantageous in spray drying processes. These neutral salts and in particular sodium sulfate are preferably used in amounts of 5 to 25% by weight.
  • the aftertreated spray-dried agents can also contain organic builder substances as further constituents.
  • organic builder substances include, for example, polycarboxylic acids or their salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these ⁇ sen.
  • polycarboxylic acids or their salts such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these ⁇ sen.
  • NTA nitrilotriacetic acid
  • sugar acids can reduce the slurry viscosity and increase the bulk density.
  • Suitable poly ere polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Terpolymers are also particularly preferred, for example those which, according to DE-A-4300772, are monomers Salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-4221 381 as mono ere salts of Acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives are included. Further preferred copolymers are those which are described in German patent applications DE 4303 320 and P 44 17734.8 and preferably contain acrolein and acrylic acid or acrylic acid salts or vinyl acetate as monomers .
  • oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the content of the organic dried substances in the spray-dried agents is generally between 0.5 and 10% by weight, preferably between 2 and 8% by weight.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers known from the prior art Phthalic acid and / or terephthalic acid or its derivatives, in particular polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • the agents can also contain components that improve solubility.
  • Such constituents are, for example, polyethylene glycols with a relative molecular mass between 200 and 4000, preferably up to 2000, but also fatty alcohols with 20 to 80 mol E0 per mol fatty alcohol, for example taig fatty alcohol with 30 E0 and taig fatty alcohol with 40 E0, but also those with the nonionic surfactants called fatty alcohol with 14 E0.
  • the spray-dried agents can include conventional foam inhibitors. These include, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8 ⁇ C24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes.
  • the salts of polyphosphonic acids which are preferably used are the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight.
  • Further constituents can be graying inhibitors, for example, which have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • water-soluble colloids of mostly organic nature are suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxyethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight. % used.
  • the agents can also contain optical brighteners, for example containing derivatives of diastostilbenedisulfonic acid or its alkali metal salts. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, contain a diethanolamino - wear a group, a methylamino group, an anilino group or a 2-methoxyethylaio group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • the content of the spray-dried granules in these components e) is preferably less than 30% by weight and in particular less than 25% by weight.
  • the aftertreated spray-dried compositions are notable for excellent washing-in behavior and also for excellent dissolving behavior.
  • conditions are simulated which correspond to a washing-in device of a household washing machine operated under critical conditions. 100 g of product are added to the test device (Zanussi induction channel). After a rest period of 1 minute, 10 liters of tap water are fed in within 80 seconds. The amount of the residue remaining afterwards is preferably less than 5 g and in particular less than 2 g for the aftertreated spray-dried compositions.
  • residues on dark textiles are simulated in two different tests.
  • Grade 3 recognizable residues which are already disturbing in the case of a critical assessment; from grade 4: clearly recognizable and disruptive residues in increasing numbers and quantities.
  • the aftertreated spray-dried agents are preferably assessed with grades less than 4.
  • the aftertreated spray-dried compositions preferably have residues of less than 10% and in particular less than 5%.
  • post-treated spray-dried detergents or components are therefore claimed, which residues in the wash-in test described are less than 2 g, preferably even less than 1 g, a residue behavior in the tub washing machine with a grade less than 4 and in the hand wash test less than 5%.
  • the post-treated spray-dried grains are processed with further components of detergents. It is particularly preferred here that the processing brings in only a maximum of 5% by weight, based on the finished detergent, of further nonionic surfactants.
  • the further ingredients which are subsequently added to the aftertreated spray-dried grain are, in particular, those which are sensitive to temperature and / or water and therefore cannot be atomized without decomposition.
  • the admixed components include bleaching agents such as peroxy bleaching agents and bleach activators, enzymes and enzyme stabilizers, colorants and fragrances, opacifiers and pearlescent agents, but also, if appropriate, foam inhibitors, in particular foam inhibitors containing silicone and / or paraffin, which adhere to a granular, are soluble or dispersible carrier substance bound in water.
  • bleaching agents such as peroxy bleaching agents and bleach activators, enzymes and enzyme stabilizers, colorants and fragrances, opacifiers and pearlescent agents
  • foam inhibitors in particular foam inhibitors containing silicone and / or paraffin, which adhere to a granular, are soluble or dispersible carrier substance bound in water.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the content of funds Bleaching agent is preferably 5 to 25 wt .-% and in particular 10 to 20 wt .-%, each based on the finished detergent.
  • bleach activators can be incorporated into the preparations.
  • Examples include N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Further known bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0525239.
  • the bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight, again in each case based on the finished detergent.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • Suitable enzymes are those from the class of proteases, lipases or lipolytically active enzymes, for example cutinases, amylases, cellulases or mixtures thereof. Enzymatic substances obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens, are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures are, for example, from protease and amylase or protease and lipase or lipolitically acting enzymes or protease and cellulase or from cellulase and lipase or lipolitically acting enzymes or from protease, amylase and lipase or lipolitically acting enzymes or proteases , Lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolitic enzymes of particular interest. Peroxidases or oxidases can also be used.
  • the enzymes can be adsorbed on carrier substances and / or embedded in Hü11 substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight, in each case based on the finished detergent.
  • the salts of polyphosphonic acids already mentioned come into consideration as stabilizers, in particular for per-compounds and enzymes. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • the other ingredients of detergents with which the post-treated spray-dried component can be processed also include other builder substances.
  • these further builder substances are, however, free of zeolite.
  • the preferred further builder substances include inorganic silicates such as crystalline layered silicates, amorphous silicates or compounds composed of amorphous silicates and carbonates, but also organic builder substances such as citric acid / citrate or Sokalan DCS ( R ).
  • Preferred crystalline layered sodium silicates are those of the general formula NaMSi x ⁇ 2 ⁇ + i'-yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the given formula are those in which M represents sodium and x assumes the values 2 or 3.
  • the amorphous silicates or silicate-containing compounds can have been produced by spray drying, granulation and / or compacting, for example by roller compaction. Some of these silicates and granates containing carbonate and silicate are available as commercial products. Reference is made here, for example, to the commercial products Britesil ( R ) from Akzo & Nobel, Nabion l ⁇ ( R ) from Rhönen-Poulenc, Gransil ( R ) from Colin Stewart or Dizzil ( R ) G from Akzo & Nobel. These further builder substances are preferably used in amounts of 5 to 20% by weight, based on the total detergent.
  • the content of the aftertreated spray-dried component in a detergent prepared in this way is at least 55% by weight of the total detergent.
  • the rinsing behavior and the dissolving behavior or the residue behavior of the processed detergents are in the same preferred ranges as were given for the aftertreated spray-dried component.
  • the detergents according to the invention can be dosed, for example, via a dosing aid directly for use in the washing drum, or via the induction device of commercially available washing machines. Since the detergents according to the invention are those which have both excellent washing-in behavior and dissolving behavior, in a further embodiment of the invention a method for washing white and / or colored textiles is preferred, a detergent according to the invention or a component for this purpose, metering is carried out via a washing-in device provided for this purpose in a commercially available washing machine.
  • Agent M1 according to the invention was prepared by aftertreatment of 69.8 parts by weight of a spray-dried product P1 of the composition given below with 4.5 parts by weight of a with 7 EO.
  • an agent VI with the same composition as Ml but containing 64.5 parts by weight of a spray-dried and untreated product in admixture with 9.8 parts by weight of a pre-mixture of 83 was obtained % By weight of sodium carbonate and 17% by weight of C12-Ci8-fatty alcohol with 7 EO (the remaining nonionic surfactant was contained in the spray-dried product), and also an agent V2 likewise with the same composition as Ml, but containing 54.6% by weight Parts of a spray-dried and untreated product mixed with 19.7 parts by weight of a carrier grain impregnated with Ci2-Ci8 ⁇ fatty alcohol with 7 EO, which consists of 54.6% by weight of zeolite A (anhydrous active substance), 1.5% by weight .-% tallow fatty alcohol
  • Two detergents M2 and M3 were produced, which contained the spray-dried components P2 and P3, 57.5 parts by weight of P2 and P3 initially containing 3.8 parts by weight of Ci2-Ci8 fatty alcohol with 7 EO and C12-C18 fatty alcohol were post-treated with 5 EO and then with 14.2 parts by weight of Nabion l ⁇ ( R ) (commercial product from Rh ⁇ ne-Poulenc) or a spray-dried soda-silicate compound of 20 parts by weight Perborate tetrahydrate, 3 parts by weight of bleach activator (TAED), 1 part by weight of enzyme granulate and 0.5 part by weight of a granular foam inhibitor based on silicone oil were prepared.
  • R Nabion l ⁇
  • TAED bleach activator
  • the detergent behavior and also the residue behavior were measured in the tub washing machine and in the hand washing test for agents M2 and M3 according to the invention (see Table 2).
  • the agent M2 left no residue in the induction channel.
  • the amount of detergent used was completely washed in after 8 l of the water flowing through.
  • compositions P P22 and PP33 in% wt% Compositions P P22 and PP33 in% wt%:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP95942725A 1995-01-12 1995-12-22 Detergent seche par pulverisation ou constituant pour celui-ci Revoked EP0802965B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19500644 1995-01-12
DE19500644A DE19500644B4 (de) 1995-01-12 1995-01-12 Sprühgetrocknetes Waschmittel oder Komponente hierfür
PCT/EP1995/005092 WO1996021713A1 (fr) 1995-01-12 1995-12-22 Detergent seche par pulverisation ou constituant pour celui-ci

Publications (2)

Publication Number Publication Date
EP0802965A1 true EP0802965A1 (fr) 1997-10-29
EP0802965B1 EP0802965B1 (fr) 2000-04-12

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US (1) US5948747A (fr)
EP (1) EP0802965B1 (fr)
JP (1) JP3841431B2 (fr)
AT (1) ATE191742T1 (fr)
DE (2) DE19500644B4 (fr)
ES (1) ES2146796T3 (fr)
WO (1) WO1996021713A1 (fr)

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US6265570B1 (en) * 1998-11-05 2001-07-24 National Starch & Chemical Investment Holding Corporation Cold water soluble starch aldehydes and the method of preparation thereof
DE19859729A1 (de) * 1998-12-23 2000-06-29 Henkel Kgaa Sprühgetrocknetes Granulat
US20030203832A1 (en) * 2002-04-26 2003-10-30 The Procter & Gamble Company Low organic spray drying process and composition formed thereby
WO2005072079A2 (fr) 2003-09-26 2005-08-11 Alza Coporation Enrobage de medicaments a charge medicamenteuse elevee et procedes de fabrication
WO2005030182A1 (fr) * 2003-09-26 2005-04-07 Alza Corporation Formulations a liberation commandee presentant un taux croisssant de liberation
WO2005030181A1 (fr) * 2003-09-26 2005-04-07 Alza Corporation Preparations a liberation regulee a base d'analgesiques opioides et non opioides
US8541026B2 (en) 2004-09-24 2013-09-24 Abbvie Inc. Sustained release formulations of opioid and nonopioid analgesics
EP2123742A1 (fr) * 2008-05-14 2009-11-25 The Procter and Gamble Company Compositions de détergent solide pour lessive comprenant du sel de silicate à faible densité
MY187405A (en) 2014-09-29 2021-09-22 Malaysian Palm Oil Board Powder form of methyl ester sulphonates (mes) and process for producing the same

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Also Published As

Publication number Publication date
ES2146796T3 (es) 2000-08-16
ATE191742T1 (de) 2000-04-15
DE59508178D1 (de) 2000-05-18
WO1996021713A1 (fr) 1996-07-18
DE19500644A1 (de) 1996-07-18
JPH10512007A (ja) 1998-11-17
US5948747A (en) 1999-09-07
DE19500644B4 (de) 2010-09-09
JP3841431B2 (ja) 2006-11-01
EP0802965B1 (fr) 2000-04-12

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